Method of making insoluble products of phenol and formaldehyde.



. is a specification.

' UNITED STATES, PATENT cl rion.

LEO H. BAEKELAND, F .YONKEBS, NEW YORK.

msrnon or MAKING INSOLUBLE raonuc'rs or rrreuon AND ronmnnmr,

No Drawing.

To all whom it may concern:

lle it known that 1, Leo II. Barnes/mo, a citizen of the Umtcd States, residing at.

Snug llock,,.'llarmony larlc, Yonkers, in

the county of \\"estchester and State of New York, have invented certain new and useful lmprovemeutsin Methods of Making lit-- soluble Condensation lroducts'ot lhenols aml l ormaldchjyde, of which the following in my prior application Serf No. 358,156, iiled l ebruary lb, 190?, l have described and claimed a method of indurating, librous or cellular .materials which consists in impregnating or mixing them witha phenolic body and formaldehyde, and causing the same to react. within the body of the material to yield an insoluble iudurating condensation Jn'otlnct, the reaction being accel esn'cd by the use of heat or con erutcd it (lensing agents. in the course of this reaction considerable quantities of water are produced, and a drying operation is resorted to to expel it.

The present. inreution relates to the production of hard, insoluble and infusible condensation products of phenols and formaldehyde.

ln practicing the invention 1- react upon.

a phenolic body with formaldehyde to obtain a reaction n'odnct which is capable of transfornmtion y heat into an insoluble and in fusible body, and then convert this reaction product, either alone or compounded with a suitable lilling material, into such insoluble and inl'usiblc body by the combined action of heat and pressure. Preferably the water produced during the reaction or added with the reacting bodies is separated before hardening the reaction product. By proccedim in this manner a more complete control of t-hc reaction is secured and other important advantages are attained as hereinafter set forth.

If a mixture of phenol or its homolognes and formaldehyde or its polymers be heat ed, alone or in presence 0 catalytic or condensing agents, the formaldehyde being present in about the molecular proportion required for the reaction or in excess thereof, that is to say, approximately equal volumes of commercial phenol or cresylic acid and commercial formaldehyde, these bodies react upon each other and yield a product consisting of two liquids which will sop Bpeetne atloa 01 Letters Eaten t. I Iatentcd Dec. '7', 1909.- Application filed July 1:, 1907, Serial no. .aaam.

arate or stratif on standing. The lighter chemical condensation or dehydration. The

liquids are readily separated, and the aquc-- ous solution may be rejected or the water may be eliminated by eyaporation. 'l'he oily liquid obtained as above'described is found to be solublein or miscible with alcohol, acetone, )henol and similar solvents or mixtures of the same. This oily liquid may be further submitted to heat: on a wateror steam-bath so as to thicken it sli htly and to drive otl' any water which mig it still be mixed with'it. If the reaction be permitted to proceed further the condensation product may acquire 'a more viscous character, becoming gelatinous, or semi-plastic in con-- sistcnce; "l'hisanodifimtion of the' roduct is insoluble or incompletely soluble 1n alcohol but soluble or partially soluble in acetone or in a mixture of acetone and alcohol.

The condensation product having either the oily or semi-plastic character may be subjected to furthcrtreatment as hereinafter dcscribed.- By heating the said condensation product it is found to be transformed into a. hardbody, unaffected by moisture, insoluble in alcohol and acetone, infusible, and resistant to acids, alkulies and almost all ordinary reagents. This product -is found to be suitable for many purposes, and

may be employed either alone or m admix- 'ture with other solid, scmrhqmd or 11 uid materials, as for instance asbestos 6 r, wood fiber, other fibrous or cellular mate rials, rubber, casein, lamp black, mica, min-- eral powders as zinc oxid, barium sulfate,

'etc., pigments, dyes, nitrocellulose, abrasive materials, lime, sulfate of calcium, graphite, cement, powdered horn or bone, pumice stone, talcum, starch, colophonnun, resins or gums, slate dust, etc., in accordance with the particular uses for which it isintended, and in much the same manner as india rubber is compounded with the above-named and other materials to yield various valuable 'products.- In compounding the condensation or dehydration product in this manner, the desired materials are mixed with the same before submitting. it tothe final hardening operation below described.

two hours or less a hard, compact, perfectly homogeneous mass similar in its properties to hard rubber or to ivory, insoluble in alcohol, acetone, and resistant to heat or infusible, and resistant to moisture and most chemical reagents as above described. In

case the-)roduct be. first mixed with asbestos. liber, ru ber, powdered substances or other materials as above described, and heat be thereafter applied av compound is obtained iiithe form of hard masses containing the insoluble condensation product described. Such masses may be produced directly in any desired form by the use of a suitable mold, or they may be produced .iii a block or irregular mass which may be cut, sawed, turned or otherwise manipulated to any suitable form or size.

Small pro ortions of solvents may be added to the initial condensation product in order to facilitate the compounding or mixing of the same, the resulting mixture being then submitted to the final baking or hardenin process as described.

While I have indicated above a practical hardening temperature of 110140 C. it should be understood that higher temperatures may be employed, in which case the time required for the hardenin process is considerably reduced; the hardening may also be conducted at 100 C. and even at lower temperatures, moreparticularly for impregnating fibrous or ce lular materials, but in this case the hardening is found to be very slow and some days may be required for its completion. The hardening may be greatly accelerated by adding small proportions of catalytic. agents, or so-ealled condensing agents, as for instaneezinc chlorid,

other metallic chlorids, acids or salts. In case such condensing agents are added the hardening occurs rapidly at relatively low temperatures.

The mode of application or compounding of the condensation product willof course depend upon the results sought. I or treating or indurating wood, the surface only may be treated, or it may be treated throughout its mass substantially as described in my copendin application above referred to; the treated material is thereafter submitted to heat, some condensing agent being added if desired. For facilitating the penetration of wood or the like the condensation product may be slightly heated to render it more 'mobile, or small iroportions of suitable solvents may be added.

- The linal heating or baking by which the condensation product, alone or compounded, is converted into an insoluble body should be etlected in aclosed vessel in case the temperature exceed 90-100 0.; without this n-ecautiou. vapors of formaldehyde and the like escape causing foam and air bubbles; furthermore theloss of the reagents and the disturbance ofthe proportions bet ween then'i )revents obtaining a product of maximum hardness and uniform texture. in a closed vessel under pressure the (meratiou proceeds with precision, and a uniform result may be always obtained.

Instead of ordinary phenol I may use cre- -sol and its homologous, -or other phenolic bodies. If desired I may employ in place of commercial forimihlehyde a solution of anhydrous formaldehyde in phenol, or the polymer of formaldehyde which on heating splitsup into anhydrous formaldehyde, may be used. 1

The initial oily, viscous or semi-plastic condensation product. may be obtained in various ways, as for instance by dggcstin a suitable mixture of phenol and ormal ehyde in an autoclave, or merely by boiling a mixture of the same in an open' vessel provided with a return condenser in order to avoid loss and variation of proportions.

.very small proportion of mineral or organic acid, or of zinc chlorid, calcium chlorid, or

other salt or agent favoring condensation may be added to the mixture, the proportion being-in all cases so small as to avoid such energetic reaction as will not permit the iiitern ediate oily, viscous or semi-plastic condensation iroduct to be obtained. Or I may add a solid salt as for instance calcium chlorid to the mixture of phenol and formaldehyde in which case the calcium chlorid immediately absorbs water and forms two dis-' tinct layers, the lower one being formed by a very dense aqueous solution of calcium chlorid, the upper one by the dehydrated inix-.

ture.

I claim:

1. lie method of producing a hard, conipact, insoluble and iutusible condensation product of phenols and formaldehyde, which consists in reacting upon a phenolic body with formaldehyde, and then converting'the .roduct into a iard, insolubleand infusible Body by the combined action of heat and pressure.

2. The method of making articles containing an insoluble and intusiblc condensation product of phenols and formaldehyde, which consists in reacting on a phenolic body with formaldehyde, producing thereby a reaction roduct capable of transformation by heat into an insoluble and-infusible body, forming the article from said reaction product,

ing the article from said reaction product,

and rendering the article hard, insoluble and infusibl'e by application of heat and pressure.

3. The method of making articles containing an insoluble and iufusible comlensation product of phenols and formaldehyde, which consists' in reacting on a-phenolic body with formaldehyde, pr ulucin; thereby arcaction n'oduct capable of transformation by heat llllO an insoluble and infusiblc body, separating i'ater from the resulting product, formand rendering the article hard, insoluble and infusible by application of heat and prcssure.

-l. The method of making articles containiug an insoluble and infusible condensation 1 product. of phenols and formaldehyde, which 'mnslsts in reacting on a phenol lC body with formaldehyde, producmgthereby a reaction ing the article from said reaction product compounded with a' tilting material, and rendering the article hard, insoluble and infusibleby application of heat and pressure.

5. Ina method of making articles coutain inc an insoluble and infusible coiulensation product of phenols and formaldehyde, the step which consists in causing the water to separate from the mixture of a phenolic body and an aqueous solution of formaldehyde by adding to said mixture a metallic salt soluble in water and adapted to cause such separation. i

.l n testimony whereof, I allixany signature in presence of t\ 'q witnesses. 'LEO 1L BAEKELAND. Witnesses: Face R. Caner,

llama S. Taiwan! 

